CN105247728B - The system for inhibiting the supplement of metal accumulation and enhancing performance and delivering the supplement - Google Patents

The system for inhibiting the supplement of metal accumulation and enhancing performance and delivering the supplement Download PDF

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CN105247728B
CN105247728B CN201480030287.0A CN201480030287A CN105247728B CN 105247728 B CN105247728 B CN 105247728B CN 201480030287 A CN201480030287 A CN 201480030287A CN 105247728 B CN105247728 B CN 105247728B
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supplement
energy
storage battery
battery
insulation piece
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CN105247728A (en
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约翰·C·菲特
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    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/08—Selection of materials as electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/06—Lead-acid accumulators
    • H01M10/12—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/42—Methods or arrangements for servicing or maintenance of secondary cells or secondary half-cells
    • H01M10/4235—Safety or regulating additives or arrangements in electrodes, separators or electrolyte
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/10—Primary casings, jackets or wrappings of a single cell or a single battery
    • H01M50/116—Primary casings, jackets or wrappings of a single cell or a single battery characterised by the material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H01M50/414—Synthetic resins, e.g. thermoplastics or thermosetting resins
    • H01M50/417—Polyolefins
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/449—Separators, membranes or diaphragms characterised by the material having a layered structure
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2300/00—Electrolytes
    • H01M2300/0002—Aqueous electrolytes
    • H01M2300/0005—Acid electrolytes
    • H01M2300/0011—Sulfuric acid-based
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The present invention relates to the supplements for inhibiting metal accumulation and separation or the synthesis of enhancing performance being used in combination for chargeable electrochemical energy storage cell or with chargeable electrochemical energy storage cell, and the system of the delivering supplement, the system comprises plastic products, the product containing plastics, the product similar to plastics, plastic containers, device, porous electrode, liquid and electrolyte, product especially relevant to the chargeable electrochemical energy storage cell for mixing one or more supplements, device, electrode, insulating trip, liquid and electrolyte.A effective amount of supplement typically exhibits the blistering of electrolyte, provides the active visual beacon in the metal deposit on each surface that the metal deposit on each surface for making chargeable electrochemical storage cell is decayed and thus reduces chargeable electrochemical storage cell.

Description

The system for inhibiting the supplement of metal accumulation and enhancing performance and delivering the supplement
Cross reference to related applications
This application claims the priority for the U.S. Provisional Patent Application No. 61/829,517 that on May 31st, 2013 submits.
Technical field
The present invention relates to the systems of the supplement for inhibiting metal accumulation and enhancing performance and the delivering supplement.This Invention includes the plastics for chargeable electrochemical energy storage cell or the supplement being used in combination with chargeable electrochemical energy storage cell Product, the product containing plastics, the product similar to plastics, plastic containers, device, porous electrode, liquid and electrolyte, especially It is product, device, electrode, liquid and the electrolyte for mixing one or more supplements.Supplement of the invention is characterized in just In making electrolyte generate foaming, as making on each surface of battery the metal deposit of (for example, on its negative electrode) decline Subtract and thus reduce active visual beacon in metal accumulation.It particularly, is typically for the supplement product of subject matter Porous insulation body between the positive electrode of electrochemical cell and negative electrode is set.These are the structures of ion porous, but by being situated between Electric material is prepared to prevent the short circuit between electrode.
Background of invention
The chargeable electrochemical energy storage cell of encapsulation in a plastic housing has become very common.It is in fully charged shape There is PbO under state2Positive electrode and Pb- negative electrode, the electrode is by dilute H2SO4Electrolyte surrounds.Pass through the porous of suitable form Insulant prevents the physical contact between electrode.There are about 1,000,000,000 six batteries configurations using in the whole world, is mainly used for It start-ups a car engine.Battery configuration based on substantially the same chemical process that there are many other, the battery are configured to negative It carries in balanced application and is signaling and illuminating in application electric car outside drive chamber's interior room；Telephone exchange；Family, office Room and industrial equipment；Computer；Server etc..
The complaint of user includes all difficulties that usually encounter in the operation of these chargeable energy-storage batteries and too Common unpredictable and limited Acceptable life.More specifically, due to for driving the energy-storage battery of car category old Change, therefore the decline of its end of charge voltage, (gassing) rate of deflating increase, temperature and water consumption rise.In normal use In, battery is subjected to the cumulative bad corrosion function of charging current, which gradually destroys the complete metal of positive electrode Support construction leads to the PbO of positive electrode2It is detached from support construction, as a result the energy storage capacity of battery is gradually lost, and finally makes electricity Pond is not suitable for normal use.
At " CRC Chemical Physics handbook ", David R Lide is edited, the 83rd edition, (2002-2003), the 1st chapter Section 4 (" CRC Handbook of Chemistry and Physics",Editor David R Lide,83rd Edition, (2002-2003), Section 4, chapter 1) in provide the element and compound to play an important role in the present specification Comprehensive description, the element and compound include the compound containing element B a, C, Cd, Cu, H, K, N, O, Pb, S, Sb, Sn.
Prior art summary
Traditionally, about 1~12wt% is used by using the metallic alloying of the building in positive electrode support construction Sb, typically using the Sb of 2.75wt% and remainder is mainly Pb to reduce charging current to positive electrode support construction Destruction.The percentage of Sb is higher, and the durability of the energy-storage battery provided is higher, but water consumption is also significant higher.
The significant drawback of Pb-Sb alloy is that Sb tends to from the support construction of positive electrode dissolve out and is electroplated onto negative electrode On active lead (Pb), wherein the Pb of the Sb and stop that reach form small electrolytic cell.This causes Pb to be converted into PbSO4And hydrogen It is escaped from Sb, negative electrode is made gradually to discharge.The effect is referred to as Sb " poisoning " in the industry.
Also the destruction of charging current is reduced by applying limitation to maximum charging voltage.This, which may have, is not intended to Effect, including be considered as permanent PbSO in electrode4Accumulation, be difficult to when so that battery is rarely employed even can not be to storage Energy battery recharges.
It is designed to offset disclosed and other limitations for perceiving and many enhancing performances for being not intended to characteristic auxiliary Means have been directed to chargeable energy-storage battery and have proposed and used a similar century in chargeable energy-storage battery.It removes Confirm its unsatisfactorily solve it is most common and therefore main user complain other than (i.e. limited service life), The overwhelming majority is well-known in the industry and does not need to refine.
The expected benchmark of service life has been kept for decades do not change, and is maintained at 800 shallowly for leisure grade energy-storage battery Circulation, is maintained at 1500 deeper cavities for technical grade.
Have been obtained for satisfactory performance in the building of shallow circulation and deeper cavity energy-storage battery, the shallow circulation and Deeper cavity energy-storage battery include from rubber tree (Hevea brasiliensis) obtain, processing and cured form it is natural suitable Formula-polyisoprenoid thermo-setting elastomer.The specific thermosetting property elastic body active will be with the high porosity titanium dioxide of concrete form Then silicon and optionally various other combinations of materials squeeze out and solidify to generate for providing separation between energy-storage battery electrode High porosity insulating trip.
It is believed that the certain compound poles being naturally present in elastomer slowly move in electrolyte and with such as lower section Formula is reacted: the decaying of the Sb " poisoning " of negative electrode and the decaying of dendritic growth is provided, and other benefits are provided, including End of charge voltage increases；And outgassing rate, temperature and water consumption reduce and the Acceptable life of energy-storage battery is obvious Increase, but the importance of the last advantage seems to be ignored by manufacturer.
The advantageous electrochemistry attenuation effect of elastomer is by the researcher in the field by using for comprising mentioning The cyclic voltammetry for taking the electrolyte of object to carry out confirms that the extract passes through in water or dilute H2SO4Middle heating is handled and is solidified Elastomer sample obtain.The identity of the part of decaying is provided and is responsible for the mechanism of decaying it is reported that still unknown.In fact, It is not yet successful to the effort for identifying that any specific compound relevant to natural thermosetting elastomer carries out.For example,Et al. United States Patent (USP) 5,221,587 in state: " mechanism is unknown and it can not explain this hair completely Bright success." (the 2nd column, 45-50 row；3rd column 66-67 row).
It is old in No. 20120270110 U.S. Patent Publication disclosed on October 25th, 2012 of Waterhouse et al. State " the definite property of the active constituent in cured [thermo-setting elastomer] particle is unknown ... " (the 0024th section).
Stated in another document of the effect that the natural thermosetting elastomer of discussion accumulates metal " ... it is related to natural [thermo-setting elastomer] inhibits the mechanism ... of the ability of the effect of [Sb] to be not well understood." (the natural thermosetting of mixing Property assessment of the elastomer-polyethylene products relative to independent polyethylene and independent natural thermosetting elastomer, referring to Www.mplp.com/TechSheets/cellforce.pdf, page 3).The document attempts by by natural thermosetting elastomer Some limited successes the advantages of obtaining natural thermosetting elastomer, are obtained with polyethylene blend.It is interesting that it is also old It states and " has attempted to include that the several methods of chemical addition agent ... or other specific coating is added in history to simulate the natural [heat Solidity elastomer] effect.These trials produce short-term active and/or harmful voltage effects ... ".
The significant drawback of elastomer is its procurement cost, and procurement cost ratio is by such as polyethylene and igelite at present The product of preparation is 3 to 4 times high.
Have another disadvantage that natural thermosetting elastomer product can be inconsistent with its activity, the reason is that chemical composition can be with Changed according to the natural trend that can occur during growth cycle.Process variations can also be to may be living source The concentration of unknown chemical constituent has influence.
Goal of the invention
The main object of the present invention is to find the method for meeting or surmounting the benefit provided by natural elastomer, described natural Elastomer is obtained from rubber tree (Hevea brasiliensis) by artificial or synthesizing mean, thus provide it is at least of equal value but It is preferred that the decaying of the Sb " poisoning " at more superior accumulator activity surface such as negative electrode, more superior deflation, are put at water consumption certainly The cumulative damage of the decaying of electricity and dendritic growth, raising and the more superior structure to positive electrode at the top of charged electric potential is made Decaying.
Object of the present invention uses the inhibition for being delivered to electrochemical energy storage cell any one of through a variety of ways The supplement of metal accumulation realizes, the supplement suitable for chargeable electrochemical storage energy battery and be suitable for The battery of chargeable electrochemistry consumption energy, the battery contains acidic electrolyte bath, at least one positive electrode and at least one is negative Electrode.Battery is adapted to receive electric current, and negative electrode makes a response electric current, with emergent gas and receives the ability of metal. Although supplement may be used as the isolate of the cis-polyisoprene thermo-setting elastomer since rubber tree acquisition to obtain, But it considers expense of the elastomer as raw material, is preferably for economic, business and most realistic purpose, the supplement The reactive compound of synthesized form as discussed further below, and also comprise in active analogue thereof, derivative and structure Similar compound.Term " isolate " or " separation " be intended to include isolated single compound or separation one group of chemical combination Object, for example, can be by extracting or other manufacturing process be obtained from natural material, because may also be by from various natural Separation is in source to obtain supplement of the invention.Term " supplement " will be understood as when referred to herein " separation or The supplement of synthesis ".Supplement optionally (because there are other approach) can be mixed to form composition with medium is retained, the group Closing object can contact with the supplement of electrolyte, modification electrolyte, to obtain bubbling character, which provides the benefit Filling object and in addition having been carried out to be enough to generate inhibits the vision of concentration of the result of metal accumulation to prove, wherein the negative electrode Supplement is made a response in operation, so that the amount of metal by its accumulation is reduced.
Detailed description of the invention
Fig. 1 is the schematic diagram for showing the two adjacent energy-storage batteries and suitable electricity constant-current power supply of electrical connection in parallel, In two adjacent energy-storage batteries, the first battery indicates treatment of battery of the invention and the second battery indicates control cell.
Fig. 2 is the image of the test device shot at the end of one week according to the program of embodiment 3.
Fig. 3 is the image of the device shot after 5 hours according to the program of embodiment 4.
Fig. 4 is the image for illustrating barbotage.
Fig. 5 is to show to be designed to provide separation, the supplement species of the invention suitable for receiving between energy-storage battery electrode The perspective view of the rib shape high porosity insulating trip of type；And
Fig. 6 is to show glass mat with adherency, provide and separate between the negative electrode and positive electrode of energy-storage battery , the plan view of a part of rib shape high porosity insulating trip of Fig. 5.
Specific embodiment
As discussed above, the object of the present invention is to provide the supplements and delivery system that inhibit metal accumulation, should Delivery system avoids the natural elastomer using the prior art, but the natural elastomer of itself and the prior art is at least shown together The performance of sample.Therefore, it is necessary to establish the characteristic of the natural elastomer for comparing.
The natural elastomer of the conventional fresh outflow from rubber tree normally produced is soliquid, the colloidal suspension Liquid includes the solid material of 30-35%, and the solid material is made of cis-polyisoprene main but non-excludedly.Also report The solid material include 2.4% neutral lipid (1% mainly glycolipid and phosphatide and a small amount of galactolipid and sphingolipid), 2.2% protein, 0.4% carbohydrate, 0.2% ash content and 0.1% other compounds.Relative concentration is according to age of tree and asexual numerous It grows, soil, weather, outflow frequency, the variation such as subsequent processing.
After numerous studies, it is believed that may be responsible for providing the decaying of the Sb " poisoning " of negative electrode；Deflation, water consumption, from The decaying of electric discharge and dendritic growth；The decaying of raising at the top of charged electric potential and the cumulative damage effect to positive electrode structure Part, be primarily present in 1% glycolipid and phospholipid moiety, more specifically, in terms of being considered the phosphatide of the part.
Phosphatide is a triglyceride replaced by phosphate-choline arrangement in fatty acid chain.The component of phosphatide includes Hydrophobic tail and hydrophilic head.Hydrophobic tail is made of two fatty acid hydrocarbon chains.Hydrophilic head is by close to middle part Glycerol " skeleton ", followed by phosphate and finally in choline (the being ethanol amine once in a while) composition of end.
Choline is similar to quaternary ammonium salt structure.It is cationic, it is meant that it carries positive charge.Phosphate be anion and And carry negative electrical charge.In biotic environment, phosphate is dominant.In Strong acidic electrolyte environment, phosphate be actually in Property and it is dominant in terms of positively charged quaternary ammonium salt.
Glycolipid is in addition to being similar to phosphatide other than phosphate and choline position have sugar.Sugared aspect can be in acidic electrolysis Positive charge is obtained in matter environment.Glycerophosphatide is the derivative of phosphoglycerol, and it includes at least one for being connected to glycerol moiety O- acyl group or O- chain -1'- alkenyl residue.
Seem that going out to enter the glycolipid of electrolyte and phospholipid fraction from elastomeric mobility is considered being connected to solid objects (especially Metal) surface, such as the surface of negative electrode.Phospholipid molecule, for example, more or less presenting to cylinder and with it closest to institute State the head alignment on surface, and its tail portion is most of perpendicular to outwardly protruding.This aspect of quaternary ammonium salt behavior is by surface Reason, personal nursing and disinfectant expert better understand.There is balance simultaneously moving to electrolyte and migrating out between electrolyte And the concentration of the lipid composition in electrolyte keeps relatively low, although it is about 1-2ppm (hundred a ten thousandths) that possibility is non-excluded. The concentration of several ppm be considered as it is highly effective, the concentration of thousands of a ppm and the higher order of magnitude be likely to it is suitable its Instead.
The solubility of the phosphatide discharged by the elastomer determines after being immersed in the water elastomer, such as using correction To hexadecyltrimethylammonium chloride water process spectrophotometer (Hach model DR/2010-Test 401) through quaternary ammonium salt The relative concentration of aspect measurement is more than 5ppm.The N- alkyldimethylbenzylammonium very similar with hexadecyltrimethylammonium chloride Ammonium chloride and phosphatide provide the decaying of the decaying of the similar dendritic growth on negative electrode and " poisoning " of negative electrode.
Application and performance of the n- zephiran in energy-storage battery are described in the U.S. of Fitter et al. The United States Patent (USP) 7 of patent 6,635,387, the United States Patent (USP) of Fitter 6,821,681 and 6,899,978 and Fitter et al., 147,972, entire contents are incorporated herein by reference.When battery is approaching or at fully charged state, for dredging for molecule Trend existing in terms of aqueous tail portion or hydrocarbon is to attract and retain one released during the charging process by the negative electrode of energy-storage battery Hydrogen partial.
It is very small and due to the surface tension in the water of electrolyte, the hydrogen since the hydrogen gas bubbles that negative electrode is released Gas bubble can be under the very high pressure more than 30 atmospheric pressure.It has calculated when the voltage being applied on battery is in battery When more than deflation potential, the felt being made of the bubble of one layer of nano-scale dimensions is formed on the surface of negative electrode.The felt exists It is that porous-permission hydrogen ion (being provided by hydrogen ion) passes through and reaches negative electricity in its degree for forming selective barrier Pole, and the hydrated cation of most of much bigger Pb, Sb and other cations being likely to be present in electrolyte is prevented to arrive Up to negative electrode.The effect of the barrier seems from reverse osmosis equipment envelope barrier without different.The residual gas that can produce and discharge Occur in the form of charging normal blistering.
Barrier hinders the hydrogen ion of higher flow rate more and more, to realize a degree of self-control.Institute Barrier is stated when the voltage being applied on energy-storage battery is lower than the deflation potential of battery with little to being substantially absent, and is being applied The barrier is formed when the voltage on energy-storage battery is sufficiently higher than the deflation potential of battery.
Determined after carefully studying, although the phosphatide separated from natural materials also can be used, industry Upper preparation, artificial and synthesis phosphatide is suitable as the supplement for inhibiting metal accumulation of the invention.In either case, The cost of supplement of the invention is substantially less than the poly- isoamyl two of natural cis-with the processing and cured form that obtain from rubber tree The relevant cost of alkene thermo-setting elastomer.
N- zephiran can improve the expected service life of energy-storage battery significantly.However, its screen Barrier just becomes effective when at least about 2.45 volts of potential is applied to energy-storage battery.Chloride counterions concentration is when lower Can be enough to interfere the function of energy-storage battery and battery it is amp- when capacity can reduce up to 3%.It is reported that thinking these Feature carries technical disadvantages and possible commercial drawbacks either individually or in combination.
It is carried just including the amphoteric surfactant of alkyl betaine and alkyl sulfo betaines (alkyl sultaine) Charge and negative electrical charge, wherein positive charge is quaternary ammonium salt, therefore the amphoteric surfactant does not have counter ion, and the amphoteric surface is living Property agent seem not as good as can it is expectable effectively.Positive charge and negative electrical charge are accommodated in the molecule with the sequence opposite relative to phosphatide. Amphoteric surfactant with the charge accommodated with sequence identical with phosphatide is satisfactory.Carry negative electrical charge yin from Subtype surfactant seems there is limited effect.
The typical but unrestricted example of suitable material or supplement is [alkyl poly(ethylene glycol) is poly- (propylene glycol)].Its General molecular structure is CH3(CH2)x(OCH2CH2)y(OCH2CHCH3)zOH, wherein x, which is usually but is not limited to 7 to 29, y, is usually But non-excludedly be 0 to 35, and z be usually but it is non-excluded be 0 to 10.The molecular structure expresses difference, such as CH sometimes3 (CH2)mCH2O(CH2CH2O)n(CH2CHCH3O)pH.Comprising be approximately similar to the molecules of these general molecular structures, its homologue, The molecular structure of glycolipid and phosphatide, the molecular structure of quaternary ammonium salt and the substance of their combination, it is likely that be suitable for use in practice The present invention.Generally, the supplement for separating or synthesizing corresponds to the latex component obtained from rubber tree rather than polyisoprene Ingredient.Therefore, the supplement for separating or synthesizing can be selected from phosphatide, alcohol ethoxylate, fatty alcohol alkoxy compound, alkane Base glycerol phosphocholine and their combination, or can be the phosphatide with choline and phosphoglycerol as head base, or tool There are the choline and phosphoglycerol as head base and at least one saturated fatty acid and at least one unsaturated fatty acid Phosphatide.The supplement for efficiently separating or synthesizing may include the C8-18 fatty alcohol with six to 30 ethylene oxide, or tool There are six the C8-10 fatty alcohols of ethylene oxide, or can be the C16-18 fatty alcohol with 30 ethylene oxide.It can be used for this Invention effective supplement can be selected from many compounds and substance, for example, selected from phosphatide, with as head base choline and The phosphatide of phosphoglycerol, with eight or more fatty alcohols, the fatty alcohol with eight or more and ethylene oxide, tool Have the fatty alcohol of eight or more and ethylene oxide and propylene oxide, alcohol ethoxylate, fatty alcohol alkoxy compound, There are six tools or more the fatty alcohol of ethylene oxide, has 30 at the C8-18 fatty alcohol with six to 30 ethylene oxide The C16-18 fatty alcohol of ethylene oxide, the latex component obtained from rubber tree rather than polyisoprene content, with phosphatide phase Same sequence accommodates the alkyl amphoteric surfactant and their combination of charge.
Specific example [CH3(CH2)11][(OCH2CH2)6][OCH2CHCH3)3] OH and [CH3(CH2)15][O(CH2CH2)30] OH is preparing the product being used for incorporation into battery and is realizing inhibition metal accumulation function of the invention for electrolyte It is satisfactory.The numerical value of above-described x, y and z are to be likely to indicate average value, will typically encounter in practice Natural number.
It the position of polyethylene glycol and polypropylene glycol moieties can be reversed or alternating.Linear or branched alkyl group phenol polyethylene glycol/ Polypropylene glycol, chain alkyl amine, alkylamine ethylene glycol and propylene glycol, alkyl ethoxylate, propoxylate, polysorbate It is suitable with various other similar complicated hydrocarbons.Animal, plant, raw material derived from mineral oil or coal can be used.In general, It can choose a variety of CH3(CH2)xOH, straight chain, the molecule containing phenol of branch or similar molecule are for the present invention, big At a temperature of about 150-200 DEG C, under the pressure that moderate improves and in the presence of KOH or similar hydroxide and epoxy second Alkane and/or propylene oxide reaction.
Be selected as the molecule of the preferred compound of supplement-OH end group or polarity in terms of in the typical low pH of electrolyte Lower acquisition positive charge (- OH+H=-OH2 +).Ether or " O " key in ethylene glycol have affinity to water.At a low ph, such as although Non-excludedly at pH 0.0, it is said that the hydrophilic parts of nonionic supplement molecule are similar to the positively charged of phospholipid molecule The neck on head and hydrogen bonding.For practical purposes, the effect and phosphorus of the single hydrocarbon chain arrangement of the typical case of the molecule of preferred substance Two hydrocarbon chains of rouge molecule are suitable.The solubility of supplement can pass through incorporation proper number during preparing supplement - OH end group, more preferably ehter bond controls.For example, the number of ether or " O " key is more, it is water-soluble better.The change of these types The solubility of object in water is closed usually to imply in H2SO4Comparable or better solubility in electrolyte.Supplement of the invention Provide the in an electrochemical cell desired functional advantage substantially the same with the migration compound of rubber tree elastomer, institute Supplement is stated similarly to move in acidic electrolyte bath.Theoretically, the isolate that supplement can be used as rubber tree elastomer obtains , but in view of being likely to high expense in such separation process, supplement is preferably synthesized and is obtained from commercial source, The active transport compound identified herein simultaneously can be obtained from a variety of commercial sources.
Solubility is routinely described according to hydrophilic lipophilic balance or HLB, and HLB usually uses numeral expression, and 0 indicates not It is dissolved in water, is dissolved in oil, 10 indicate similarly to dissolve in water and in oil, and 20 indicate to be dissolved in water, do not dissolve in oil.HLB number is preferably low Supplement in about 10 will be suitable for porous electrode, especially negative electrode；And the supplement that HLB number is preferably more than about 10 will fit Plastic products for energy-storage battery, the product comprising plastics, the product similar to plastics and the container by plastics preparation.HLB Number is but non-excluded the supplement for being 12 to 18 will be suitable for electrolyte, and HLB number is at least more than 2, preferably 5 to 16 supplement The supplement that the piece for being suitable for providing separation between the electrode of energy-storage battery and HLB number are 2 to 10 by object will be suitable for more Pore electrod.
There are many techniques can be used for supplement and plastic composition of the invention, to be formed for energy-storage battery by mending The product for filling plastics preparation, the supplement product prepared by the material for being similar to plastics, the product comprising supplementing plastics, supplement plastics Container, supplement porous electrode and supplement electrolyte.Inventory can include but is not limited to following.
Product, the product similar to supplement plastics and the product comprising supplementing plastics prepared by supplement plastics, for example, by In including but not limited to below group plastics preparation product: polyethylene, polypropylene, polyethylene-polypropylene copolymer, High density polyethylene (HDPE), ultra-high molecular weight polyethylene and igelite utilize the selection that supplement is received with preferred concentration Plastics, by before processing mixing plastics in the pigment mode substantially the same with plastics hybrid mode with supplement It closes, product described in injection molding, extrusion, sintering or rotation or blow molding.Before being mixed into plastics, by the supplement Object is optionally incorporated into carrier, to encapsulate supplement.Many encapsulating materials will be known to those skilled in the art 's.In one embodiment, the carrier can be made of the dusty material that can be blended with supplement, and the carrier With plastic compatible to promote distribution in process in the plastic, the supplement of protection in process, or another Supplement in use is provided in a embodiment to discharge from the control of product.Supplement-carrier combination can be with opposite High concentration combines in product, to explain consumption during plastic processing is into product.In another embodiment In, the amount and/or composition of carrier can choose to realize supplement after chargeable electrochemical energy storage cell comes into service Time controlled released.Plastics-supplement the concentration preferably directly combined is similar to the concentration conventionally used for pigment.Experience applies heat Tens of seconds, processing temperature are most preferably below 230 DEG C, are preferably lower than 200 DEG C, preferably not less than 150 DEG C, selectively for 280 DEG C or lower.
No. 3,123,654 United States Patent (USP) of Malischewski et al. provides the detailed of the example suitable for this method Description, entire contents are incorporated herein by reference.No. 3,351,495 United States Patent (USP) of Larsen et al., which provides, to be suitable for The detailed description of another example of this method, entire contents are incorporated herein by reference.
The supplement of encapsulating is typically but non-excludedly by being blended in one for the suitable carrier and supplement of necessary amount Become homogeneous mixture to prepare, be optionally blended together with the suitable solvent being removed after mixture becomes uniformly It is prepared as homogeneous mixture.Hereafter, the supplement of encapsulating is handled to provide powder, which can be cleaned with hot water, so It dries afterwards and the powder with the particle on surface of heat polishing is provided using hot air.
By the supplement product of plastics preparation, the supplement product similar to the supplement product of plastics and comprising plastics, Ke Yiyou Such as it is plasticized or as the polyvinyl chloride that dough presents, has been prepared with the help of in solvent rather than by thermal softening.It should Then product is extruded, receive supplement before processing in the mode substantially the same with pigment, or receives predissolve or outstanding Float on the supplement of the preferred concentration in solvent.Processing temperature is preferably lower than the boiling point of water under the boiling point of water.In Witt Et al. the 2nd, 772, No. 322 United States Patent (USP) in provide the detailed description of example suitable for this method, entire contents are logical It crosses and is incorporated herein by reference.It provides in No. 4,153,760 United States Patent (USP) of Sundberg et al. suitable for the another of this method The detailed description of one example, entire contents are incorporated herein by reference.
Negative electrode can receive accompaniment of the supplement as foaming agent of roughly the same concentration.Foaming agent preferably includes It is subdivided into C and BaSO4Lignin derivative.A variety of materials mix in suitable device.Alternatively, supplement is mixed at it It is soluble in solvent before entering into energy-storage battery, and dissolved matter is applied to the electrode of assembly and makes it dry.
Before injection molding, the plastic shell of supplement can be used for using supplement as being routinely included in or be added to The accompaniment or substitute of the pigment in the plastic material of shell are prepared, is mixed with roughly the same concentration.Injection molding process With normally equally carry out.
The electrolyte of supplement can also generate in a case where, i.e., electrolyte directly receive supplement or supplement can be with It is dissolved in energy-storage battery make-up water with suitable concentration and to be suitble to interval to be added in (dose) electrolyte.Not only due to supplement It is consumed by negative electrode and it is also aoxidized by positive electrode, therefore supplement can not accumulate high-level concentration.
As described herein, suitable supplement of the invention can be incorporated into plastic products.Optionally, exist wherein It, can also be by this under some cases that a large amount of rubber tree elastomer or synthetic elastomer are mixed to the optional needs in product It mixes a bit together with supplement to provide blend, to further enhance the effect for inhibiting metal accumulation and enhancing performance.? Under such circumstances, single distinguishing characteristics reliably can for example but non-excludedly pass through H1And/or C13Nuclear magnetic resonance (NMR) Spectroscopic methodology is identified.
The Sb " poisoning " of formation and negative electrode of the skeleton (dendrite) on negative electrode is the embodiment of plating.Work It is actually identical as the mainly business plating of acidic electrolyte bath by being commercially used for generation metal particle to make mechanism.It is heavy Product object can be powdery, threadiness, spongy, granular and/or moss shape.Pb-Sb metal alloy comprising positive electrode support construction Solubility in the electrolyte is very low but is not zero.When applying enough potentials, some surface metals at positive electrode can Be converted into oxide and it is some be gradually dissolved in electrolyte after supplied for electronic, pass through electrolyte as cation To negative electrode, the cation described in negative electrode receives electronics and is precipitated as metallic crystal.Accumulation of the Sb on negative electrode increases The top for having added deflation, having increased water consumption, increase self discharge, reducing charged electric potential.Metal cation is relatively heavy, by Gradually cause bottom deposit of more metals to negative electrode.The part for reaching the metal of negative electrode can remove, and form sediment.
Plating in chargeable electrochemical energy storage cell is undesirable, but is inevitable.Come from accidental viewpoint See that it is seemingly imperceptible, therefore usually ignored.It is the accompaniment of gas evolution when charging at negative electrode. It needs to apply the potential for being sufficiently great to initiate and keeping plating.With PbO2- Pb electrode and H2SO4The typical energy storage electricity of electrolyte The inapparent gas evolution of application potential of the pond experience lower than 2.25 volts, condition, which is that negative electrode is opposite, is free of Sb；At 2.35 volts Under nearly zero plating and the evolution of visible gas, moderate under 2.65 volts but be not finally destructive plating and bulk gas Evolution, the two from 2.35 to 2.65 volts are gradually increasing.1.6913 volts of sections of the potential developed by the battery of the type are positive electricity The PbO of pole2The distinctive feature of electrochemical potential.
The of the invention supplement for inhibiting metal accumulation in electrochemical cell of the invention existing for the result is that one Supplement is divided to migrate to battery surface, especially negative electrode surface.The part can receive gas when gas is escaped from negative electrode As a result body then is the formation of barrier of the invention at negative electrode surface.From can reside in any Sb on negative electrode Escaping gas can also promote the formation of barrier.And not all cell voltage potential each contributes to the activation of barrier of the invention. Activation is by 2.25 (total cell voltage) -1.6913 (PbO2Voltage)=0.5587 voltage section.The activation of barrier is related in negative electrode The electro-chemical activity at place, the activity not being related at positive electrode.Plating is related to the electrification at positive electrode and at negative electrode Learn activity.Supplement of the invention is effective, the metal for the various metals that reservation can be used for constructing energy-storage battery With substantially similar electrochemistry and deflation potential, including but not limited to Pb, Sb, Sn, Cd and Cu.Supplement and institute of the invention Its application method stated is suitable for the electroplating cell of the wherein type using one of these metals.
Presence of the supplement of the invention of sufficient amount at negative electrode surface can be proved by following: with it is unassembled The negative electrode for having the equivalence of supplement of the invention to fill energy-storage battery entirely is compared, when applying high isostatic strength constant current charge, entirely The potential for filling the negative electrode of energy-storage battery significantly improves.
It has been found that the presence of a effective amount of supplement of the invention currently in use in the electrolyte in energy-storage battery It can be confirmed by foam, the foam at a suitable temperature, is being kept than volume of air in big at least 10 times of shell, Preferably 80 to 105kPa atmospheric pressure and about 10 to 100 DEG C at a temperature of, in a part of electrolyte or accommodate supplement In any other suitable fluid it is appropriate stirring after generate and retain, the electrolyte it is static preferably before vibration and It does not boil.It should be noted that dilute H2SO4(1.250sg) boils at 109.2 DEG C or so at ntp.Electrode in energy-storage battery is deposited In the electrolyte for gradually exhausting supplement.Therefore, the accumulation of supplement is typically via one section be suitble to before described program Electrode is separated or removed in time to promote.The presence of supplement of the invention in negative electrode can by assessment process it Preceding suitable a period of time removes all positive electrodes to determine, thereafter through generally in accordance with the process described above by vibrating institute Caused foam confirms.
It has been found that can inhibit without metal accumulation in the case where the characteristic of no any reducing foam.Think Bubble confirms the ability of supplement molecule and gas interaction, therefore is evidence but blistering existing for the supplement of effective concentration Itself contribution is had not a particle of to effect.Even only perceptible blistering is useful activity mark.
Will now be described the battery for chargeable electrochemistry consumption energy of the invention, comprising inhibition metal of the invention The preparation of the electrolyte of the sufficient amount of the supplement of accumulation.Particularly, in the battery 14 being described below, it is intended to is used for first About 100 cubic centimetres in terms of supplement-incorporation in energy-storage battery or incorporation of the invention energy-storage battery of the invention are outer The extraction of portion three-dimensional dimension part: then cleaning will be extracted part and be divided into having a size of about 10 to remove surface smut and drying Dry segment is placed in 1.5 to 2 liters of vial or inert plastic bottle and 150 millis is added by millimeter or smaller suitable segment Rise the energy-storage battery H of conventional intensity2SO4Electrolyte, such as 1.250SG.Electrolyte needs of the invention soak for a period of time and even You stir.The bottle is closed and is stored at about 30 to 40 DEG C.Pass through strenuous vibration institute above and below manual vertical once a day State bottle about 10 seconds.By repeating enough number of days (rarely exceeding 7 days), the vibration generates foam on the surface of electrolyte, It is gradually increased with continuous vibration blistering every time, is kept for preferably up to 5 seconds preferably up to foam, most preferably 5 to 10 Second, however, at the end of vibration, preferably not far more than 10 seconds and most preferably no more than 3 minutes or longer time. If (foam duration 3-5 minutes, the concentration of supplement was likely to more than work optimised quantity about 10 to 100 times.It is being electrolysed The satisfactory concentration of supplement in matter is about 1-2ppm.It can be the appropriate of excessive concentrations using general electrolyte dilution It remedies.Selectively, liquid portion can be dropped and of short duration repeated wetting.) this indicates the energy storage in routinely driving automobile Under cell condition, supplement is transferred to the fair simulation in electrolyte.It blisters imperceptible generally in energy-storage battery, the reason is that Supplement generation foam ingredient release when and the absorption at negative electrode and the oxidation at positive electrode upon release, from And provide foam attenuation.Absorption is most likely subject to limit, and oxidation is likely to continue progress.Separation with these electrolysis promotes bubble Foam generates.
For passing through delivering electricity with the big chargeable electrochemical energy storage cell of the series connection of outdoor automobile in drive chamber The ferro resonance or low power-factor transformer and rectifier of stream, thyristor or high frequency transistor power adapter charge, institute It states electric current and is prevented from destructive rising when battery discharges completely, and continue to flow when battery is close to fully charged state.This It is realized by current control.For charger it is possible that supplying gradually smaller electric current to the end of charging, but more preferably Be after deflating at 2.35 volts of each cell voltage potential and starting, controllable constant current to be supplied within suitable a period of time and is completed Rate.Gas is escaped with plating.Operating aspect and means for assessing plating degree is actually by dress described below It sets and carrys out illustration.
Business energy-storage battery is prepared using the electrode assembly for being restricted to minimum volume available, and electrode assembly is micro- by undergoing Grain is from the unpredictable material building to fall off of negative electrode and positive electrode, so that extremely being difficult to assess the front and back quality of negative electrode simultaneously Negative sediment and positive sediment are distinguished in deposition site point.For evaluation purpose, the mode of battery building needs to dismantle (tear- down).This is building and destructiveness so that the impossible unsuitable form of accurate evaluation height of the device of the invention effect Both methods.Battery for evaluation must come out actual necessity, purposeful to make.
Referring to Fig.1, which show the electrochemistry dresses for being similar to the chargeable electrochemical energy storage cell for being connected to charging unit 10 electrical schematic is set, device 10 includes constant current supply 12, the first battery 14 and the second battery 16, and constant current supply 12 is typically To adjust to deliver the electronics tune of the stable 50 milliampere electric current under the potential for typically but being not solely no more than 10 volts Control testing stand power supply.Battery 14 includes the electrolyte 18 with 100 milliliters of dispensed volumes and battery 16 includes to have 100 milliliters points Electrolyte 20 with volume.Dispensed volume can be any volume between 100 to 125 milliliters, and condition is that battery 14 and 16 connects Receive the electrolyte 18 and 20 of substantially the same volume.Electrolyte 18 and 20 is the conventional energy-storage battery obtained from identical source container H2SO4Electrolyte.Battery 14 includes positive electrode 22 and battery 16 includes substantially the same positive electrode 24, and electrode 22 and 24 passes through Conductor 34 and conductor 36 are electrically connected to each other.Battery 14 includes negative electrode 26 or processing electrode, and battery 16 includes that this is upper identical Negative electrode 28 or reference electrode, electrode 26 and 28 are electrically connected to each other by conductor 38 and conductor 40.In the operation of electroplanting device 10 In the process, electrode 22 and 26 is immersed in electrolyte 18, and electrode 24 and 28 is immersed in electrolyte 20.Pairs of electrode 22 and 26 and the submergence part substantial symmetry of pairs of electrode 24 and 28 place and at it closest to actually and having Effect ground makes electric field phase etc. substantially equally separate 18 millimeters.The building of battery 14 and 16 corresponds generally to show in the diagram The layout shown.
Electrode 26 and 28 respectively eligibly and is preferably built into be used to weld, plumber usually using type 97%Sn conducting wire (40 mm lengths, 2 mm dias) is immersed in its relevant electrolyte.Electrode 22 and 24 can be by including Other metals of Cd, Cu, Pb and Sb are individually or combination constructs.Sn conducting wire for be used as negative electrode material be preferably as Its surface has not graying bright metallic luster in air, and because at -0.1375V, than any other gold Belong to the electrochemical potential for the Pb being more closely similar under 0.1262 volt.Before electrode 26 and 28 is in incorporation battery 14 and 16 It cleans and is polished using common thin paper in acetone.
Power supply 12 provides the electric current flowed in conductor 30 and 32 being held essentially constant under 50 milliamperes.The electricity of delivering The value of stream can be any value in the 5% of 50 milliamperes be held essentially constant.The electric current flowed in conductor 34 is added and is being led The electric current flowed in body 36 is equal to the electric current flowed in conductor 30.Similarly, the electric current flowed in conductor 38 is added and is being led The electric current flowed in body 40 is equal to the electric current flowed in conductor 32.It is consistently equal to pass through by the voltage that conductor 34 and 38 occurs The voltage that conductor 36 and 40 occurs.Therefore, battery 14 and battery 16 are subjected to identical potential always.The circuit arrangement is amplification electricity The electrochemical derivatization object of " long-tail pair " on road, the British patent 482,740 (1936) of Blumlein.
It is suppressed by the electric current delivering of constant current supply 12 until received 100 measured completely milliliter electrolyte of battery 14 18 and received 100 measured completely milliliter electrolyte 20 of battery 16.Battery 14 and 16 receives it always by pouring into simultaneously manually The electrolyte of volume.Electrolyte 18 and 20 derives from same containers.
The electrolyte 18 of embodiment 1 obtains in the following manner: 150 milliliters for drawing the first volume from container, then According to said extracted, soak with foam test program prepare, later from bottle remove 100 milliliters of volumes processing electrolyte simultaneously It is placed in battery 14 to become electrolyte 18.100 milliliters of electrolyte of the second volume are drawn from container and are placed directly in To become electrolyte 20 in battery 16.Electrolyte 18 and 20 is in substantially the same temperature electroplanting device 10 when operation starts Under degree.Constant current supply 12 is opened within tens of seconds after battery 14 and 16 receives electrolyte 18 and 20.
Embodiment 1
As negative electrode 26 and 28, the Sn conducting wire of 500 millimeters of long same types of each freedom constructs electrode 22 and 24, should Sn conducting wire is rolled into circle suitably to save space.Electrolyte 18 according to above-mentioned extraction, soak with foam test program obtain and As a result preparation includes the supplement from the suitable sample comprising supplement.Battery 14 receives initially to be drawn from container 100 milliliters of parts of the electrolyte, and battery 16 receives the 100 milliliters of electrolyte directly drawn from container.Under 50 milliamperes After five hours, electrode 26 has received the transparent mist degree of light gray non-ferrous metal, and the pine tree shape that electrode 28 has accumulated metallic crystal twines Knot growth.
Embodiment 2
Electrode 22 and 24 is substantially the same with according to the electrode 22 and 24 of embodiment 1, the coil building of each free Sn conducting wire. The preparation of electrolyte 18 and 20 for the embodiment, according to for embodiment 1 extraction, soak and foam test program generate And preparation, the sample in addition to not including supplement extract, soak, blistering for providing between energy-storage battery electrode The high porosity insulating trip comprising rubber tree natural elastomer of type is separated, and uses the electrode from it.Under 50 milliamperes After five hours, electrode 26 has received the transparent mist degree of light gray non-ferrous metal, and the pine tree shape that electrode 28 has accumulated metallic crystal twines Knot growth.
Embodiment 3
Electrode 22 and 24 is respectively using 5 grams be slightly pressed into the small polyester textile cylinder supporter woven meticulously The building of Sb metal powder, the supporter assembled in advance has to be led by the inner band of the pure Pb complete length prepared and base widths Body.The Pb conductor of electrode 22 is connected to conductor 34, and the Pb conductor of electrode 24 is connected to conductor 38.Supplement by by 0.5 milli [the CH risen3(CH2)x][(OCH2CH2)6][(OCH2CHCH3)3] OH (x be 7 to 15 and including isomer) is dissolved in 99 In milliliter water, then its 1 milliliter of part is transferred in battery 14 and is prepared.Battery 16 receives 1 milliliter of fresh water.It later will be electric Solution matter 18 and 20 is poured into battery 14 and 16.The supplement concentration sealing of electrolyte 18 is 50ppm (volume).Five under 50 milliamperes After hour, electrode 26 obtains hardly perceptible coating, and retains the major part of its original bright Sn metallic luster, And electrode 28 obtains typical thin, opaque, the dark coating of Sb, and a small amount of same color is deposited in the lower part of electrode Sediment.
Under 50 milliamperes after 10 hours, electrolyte 18 receive largely with the original vol equal volume that provides and dense The supplement of degree is to compensate the oxidation of the supplement due to caused by the high surface area of positive electrode 22, and electrolyte 20 receives in equal volume Water.(electrolyte of business energy-storage battery fills in battery, formed, when getting out shipment or can during its periodic operation Similarly to receive suitable supplement).Under 50 milliamperes after 1 week, electrode 26 carries perceptible coating and retains light Some signs in pool, and portion deposited the dark precipitate objects of a large amount of volumes to electrode 28 under the electrodes.It initially include 5 grams of Sb powder The supporter of electrode 24 retains the about one third of the original vol of Sb powder.The supporter of electrode 22 retains the almost complete of Sb powder The original vol in portion.Difference is clearly.
Program carries out after starting one week.Using constant current supply rather than stiff accommodates the nature stablized in battery The potential by battery 14 and 16 of value.When current source 12 disconnects, do not drop to zero by the potential of conductor 30 and 32.Electricity Pond 14 and 16 supports PbO2-Pb-H2SO4The potential by conductor 30 and 32 of the feature of energy-storage battery, although showing limited The self discharge of storage volume and relatively high rate, however fully confirm the mechanism and plating skill of electrochemical energy storage behind The significant overlapping of art.
Embodiment 4
Electrode 22 and 24 is respectively substantially the same with the electrode 22 and 24 of embodiment 1, is constructed by the coil of Sn conducting wire.For Preparing for the electrolyte 18 and 20 of the preparation and embodiment 3 of electrolyte 18 and 20 in the present embodiment is substantially the same, in addition to electricity It solving other than the supplement concentration in matter 18, the supplement concentration in electrolyte 18 is reduced to the concentration of the 1ppm (volume) of estimation, It is realized by other intermediate dilute appropriate.Under 50 milliamperes after five hours, electrode 26 has received light gray non-ferrous metal Transparent mist degree, and electrode 28 has accumulated the pine tree shape entanglement growth of metallic crystal.
The Pb tape conductor of embodiment 3 obtains PbO in the dozens of minutes after current source 12 starts delivering electric current2's Distinctive dark-brown verdigris, so that the work positive electrode of battery 14 and 16 is effectively become, to the total electricity for passing through battery 14 and 16 Gesture contributes 1.6913 volts of parts.The Sn- positive electrode of embodiment 1,2 and 4, Sn- negative electrode arrangement are formd through battery 14 and 16 Potential, the potential correspondingly about 1.6913 volts of amount lower than the potential in embodiment 3 under 50 milliamperes.
It is the image of the control cell on the treatment of battery and right side for showing left side referring to Fig. 2 and 3.Fig. 2 was tied at one week The image of the device shot simultaneously according to the program of embodiment 3 when beam.Fig. 3 is after 5 hours simultaneously according to the journey of embodiment 4 The image of the device of sequence shooting.Examples 1 and 2 give almost same as Example 4 as a result, i.e. metal at the end of experiment The degree of accumulation is almost the same.Sn is highly soluble in acidic electrolyte bath and Sb is not readily dissolved in acidic electrolyte bath, and it is assorted for being considered as Obtain after only 5 hours in example 4 as a result, and for embodiment 3, but obtain result after one week.These figures As showing the effect for inhibiting metal to accumulate significantly using supplement of the invention fully aware ofly.Fig. 4 is to illustrate that blistering is made Image.
Embodiment 1,2,3 and 4 is provided in Pb-PbO2-H2SO4The plating type occurred in energy-storage battery operational process Accurate duplication and the device of the invention make the metal deposit on the negative electrode of such energy-storage battery decay, usually Sb, To reduce the convenience of Sb " poisoning " or the accurate duplication of ability.By by assembly of the invention provides plating in negative electrode On the reduction degree of metal deposit be defined as, be attracted to the quality of reference electrode divided by the matter for being attracted to processing electrode Amount typically but is not solely equal at least about 1.05, preferably 1.1, more preferably 2, most preferably at least 10 or higher.
It is prepared using the supplement of synthesis by product prepared by plastics (specially polyvinyl chloride (PVC)) to generate supplement Plastic products.Compared with the high porosity insulating trip prepared by natural thermosetting elastomer typically blisters, according to above general Samples with water repeated washing is then immersed in electrolyte by the program stated, and in vibration, display blistering shows the electrolyte Supplement is present in electrolyte.When sample to be placed in electrochemical cell, it is found that the operation of battery has and uses quite The identical operation advantage that obtains of the high porosity insulating trip that is prepared by natural thermosetting elastomer, to establish the present invention The serviceability in various battery components is generated in the plastics by supplementing, has the advantages that work as but do not have with natural thermosetting elastomer phase There are relative expense and consistency problem.Although describing PVC, a variety of plastics will be suitable for above, and for saying The selection PVC of improving eyesight, the present invention is not limited to be used together with PVC.
It can be the positive electricity for being typically placed at electrochemical cell in conjunction with such product of supplement of the invention Porous insulation body between pole and negative electrode.These are ion porous structures, but are prepared by dielectric material to prevent electrode Between short circuit.
Fig. 5 shows the example of such insulator.Certainly of the invention many other set can also be had benefited from by having Meter, this is the example of group.Fig. 5, which is shown, to be separated in the negative electrode of chargeable electrochemical energy storage cell with positive electrode offer Single rib high porosity insulating trip 42.Described 42 by typically but being not solely the flat of about 0.2 to 0.5 millimeters thick Face back net 44 forms.Rib 46 extends outwardly from surface 47, typically about 0.2 to 3.0 millimeter prominent.The thickness of rib 46 can be About 0.5 to 1.5 millimeter.High porosity insulating trip 42 is permeable for the electrolyte of chargeable electrochemical energy storage cell.
Described preferred orientation is vertical with rib 46, so that rib forms channel 48, channel 48 allows electrolyte circulation simultaneously And any gas generated is also allowed to escape up during the charging process.Similarly, any particle of formation can be from piece 42 Surface, which is slided, to be come.The width and length of insulator are typically less times greater than the width of electrode and length, to provide in-between All standing, back net 44 are arranged normally close to negative electrode, and rib is directed toward positive electrode.
High porosity insulating trip can optionally wrap silica containing polymer material preparation by polymer material, and And according to the present invention, also a effective amount of supplement of the invention is wherein being combined.
Fig. 6 shows the plan view of a part of assembly including rib shape high porosity insulating trip 42.By glass fibre Or polyester fiber preparation fibrofelt 50 adjoin rib 46 tip and can be in connection.Back net 44 and negative electrode 52 are neighbouring And felt 50 and positive electrode 54 are neighbouring.Although actual electrochemical cell may include other optional components, such as big envelope, pipe, metal Handguard (gauntlet) and spacer (spacer), but for the purpose of ease of explanation, these are not shown.
Assembly is submerged in the electrolyte to form chargeable electrochemical energy storage cell.Certainly, electrochemistry storage is recharged Energy battery typically comprises multiple assemblies, and each continuous electrode has at least one neighbouring insulating trip 42 and fibrofelt 50, alternate positive electrode and negative electrode, to be separated by insulating trip 42 and fibrofelt 50.And for the purpose of ease of explanation, Only show one.
The back net 44 neighbouring with negative electrode 52 is relatively distant from positive electrode 54 to promote the supplement for including in insulating trip 42 It is migrated by electrolyte to negative electrode 52.Skeleton can in the chargeable electrochemical energy storage cell of the prior art shape At metal composition that the skeleton origin is derived from positive electrode 54, being slowly electroplated on negative electrode surface 54.In battery Service life in, these skeletons form elongated ridge, which finally penetrates hole and the extension of insulating trip 42 Into channel 48.Although reaching, the dendritic crystal body portion in channel 48 generally fractures and harmless underground is dropped into battery bottom In sediment collector (trap), prevent to form short circuit between negative electrode and positive electrode, but short circuit finally is still able to occur. Have been found that presence of the supplement in insulating trip, by inhibiting metal to discharge from positive electrode, skeleton of significantly having decayed Formation, thus delay short circuit generation.
Fibrofelt 50 is arranged to reduce active material falling off from positive electrode 54.The nothing during life validity period of battery The active material particulate for penetrating to meaning fibrofelt 50 can enter channel 48, then harmlessly fall and enter the precipitating of battery bottom (not shown) in object collector (trap).
In the case where porous insulation piece is made of PVC, it can be advantageous that before being processed into insulating trip, by some benefits It fills object and is easy the material being blended with most of PVC powder to provide with PVC plastic pre-assembled.This is easily operated, and ensure that Compatibility and distribution in process.For example, the supplement of 2-30% can be dissolved in together with a large amount of PVC by weight In solvent, concentration can depend on the selection of supplement, desired amount etc. in final products.One example can be about 25%. Solvent is removed and product is grated and is classified to generate desired granularity.Powder is thoroughly cleaned, dry and is optionally added Heat is so that particle surface is secured.Wash and dry particle again optionally to provide the supplement being encapsulated in PVC (original text PCV) Object.Then the material can be blended with various desired concentration with a large amount of PVC substances for being doomed to be machined into insulating trip, and Then the material being blended is used as such as extrusioning mixture and is fed in extruder, exhausted for being generated according to known preparation step Embolium, to generate when coming into operation in chargeable electrochemical storage cell comprising the exhausted of the supplement suitable for controlling releasing pattern Embolium.
Certainly, the plastics other than PVC can be used, for example, polyethylene, polypropylene, polyolefin, polyphenyl can be selected from Ethylene, polyvinyl chloride (PVC), phenolic resin, and combinations thereof.
It may be advantageous that before being processed into insulating trip, combine with suitable polymer material suitable supplement with The pre-assembled material being eligibly blended with number of polymers material is provided.This is easily operated, allows using different types of pre- group Close and a large amount of polymer material and make any post-processing, such as the nothing of the supplement during solvent extraction technology after squeezing out Meaning, which is lost, reduces to minimum.For example, can by supplement directly with a large amount of polyvinyl chloride, polyethylene, polypropylene or any other Suitable polymer material combination, heating is until being sufficiently softened or melted, blending and cooling later.
Another example by make supplement the boiling point approaching or at pre-assembled solvent at a temperature of with a large amount of polychlorostyrene Ethylene, polyethylene, polypropylene or any other suitable polymer material are dissolved in together in pre-assembled solvent, then heat with Essentially all of pre-assembled solvent is removed, is cooled down later.It is suitable, example with the high boiling a variety of pre-assembled solvents of moderate Such as, but not limited to, cyclohexanone and decahydronaphthalenes.Amount of the supplement in pre-assembled substance can be by weight 1-40%.One Example can be 15%.
So that pre-assembled material is clayed into power and classify to generate desired granularity.The powder of classification is optionally by with for example But hot water or water-solvent mixture cleaning are not limited to process to exhaust the surface region of the classification powder particle of supplement, together When retain most of supplement of the inside, to provide encapsulating supplement in the polymeric material.The pre-assembled material and big Partial polymer material and it is doomed the other necessary material of extrusion or sintering process for being processed into insulating trip with any Desired concentration is blended.Extrusion process or sintering process are carried out according to such as, but not limited to known preparation step, thus setting The insulating trip of the supplement comprising being suitable for controlling release is generated when in chargeable electrochemical energy storage cell.
Described embodiment of the present invention will be considered illustrative rather than restrictive in all respects.This hair It is bright to be particularly described in the appended claims and what be carried out falls into meaning of the invention, equivalent, model All changes in enclosing and being spiritual are intended to include wherein.

Claims (42)

1. a kind of for enhancing the system of the performance of chargeable electrochemical energy storage cell, comprising:
The supplement of the enhancing performance of separation or synthesis, the supplement include isolated substance, the substance of synthesis or combinations thereof； With
Energy-storage battery, the energy-storage battery include shell, electrolyte, positive electrode, negative electrode and porous polymer insulating trip, and Suitable for including multiple assemblies of the alternate positive electrode and negative electrode separated by insulating trip；
Wherein, a certain amount of supplement and the energy-storage battery component in the group by forming as follows are included in together, will mend Fill object and be delivered to energy-storage battery, and treatment of battery is consequently formed: shell, electrolyte, negative electrode, porous polymer insulating trip and A combination thereof；
The amount of supplement included in together with energy-storage battery component are as follows: when under the atmospheric pressure of 80-105kPa and 10~100 The energy-storage battery components that will be suitable for being placed in acidic electrolyte bath at a temperature of DEG C are placed in acidic electrolyte bath, in acid electricity Xie Zhizhong soaks 1-7 days and is enough to generate the amount of foam when stirring by vibration, and the foam so generated shows sufficient amount Supplement is included in together with energy-storage battery component；
Wherein, when with do not have compared with the performance of the battery of energy-storage battery component supplement included in together when, it is described with Energy-storage battery component a certain amount of supplement included in together realize the treatment of battery in the group by forming as follows At least one performance enhancement: the metal accumulation on the negative electrode for the treatment of of battery reduces, the evolution of gas from treatment of battery Reduce, the water consumption for the treatment of of battery is reduced, the potential between the positive electrode and negative electrode for the treatment of of battery increases, treatment of battery just The corrosion of electrode is reduced and the self discharge for the treatment of of battery is reduced；And
Wherein component of the supplement in the group by forming as follows: phosphatide；Fatty alcohol alkoxy compound；Alkyl glycerol phosphorus Sour choline；With eight or more fatty alcohols；Latex obtained from rubber tree, other than polyisoprene content at Point；The alkyl amphoteric surfactant of charge is accommodated with sequence identical with phosphatide；And combinations thereof.
2. the system as claimed in claim 1, wherein the supplement is alcohol ethoxylate.
3. the system as claimed in claim 1, wherein when the energy-storage battery component selected is acidic electrolyte bath, and in 10- When being kept for 1-7 days at a temperature of 100 DEG C and under the atmospheric pressure of 80-105kPa, shake in the acidic electrolyte bath thus taken out one Rise when blister, blister be continued above the bright sufficient amount of 5 stopwatches supplement and energy-storage battery component it is included in together.
4. system as claimed in claim 3, wherein the supplement is comprised in acidic electrolyte bath.
5. the system as claimed in claim 1, wherein the supplement include obtained by rubber tree, in addition to polyisoprene Latex component outside ingredient.
6. the system as claimed in claim 1, wherein hydrophilic-lipophilic balance (HLB) (HLB) number of the supplement is greater than 2.
7. the system as claimed in claim 1, wherein the supplement also include by rubber tree obtain natural cis-gather it is different Pentadiene thermo-setting elastomer.
8. the system as claimed in claim 1, wherein the supplement includes with the choline and phosphoglycerol as head base Phosphatide.
9. the system as claimed in claim 1, wherein the supplement include with as head base choline and phosphoglycerol simultaneously And the phosphatide at least one saturated fatty acid and at least one unsaturated fatty acid.
10. the system as claimed in claim 1, wherein the supplement includes the C8-18 rouge with 6 to 30 ethylene oxide Fat alcohol.
11. system as claimed in claim 10, wherein the supplement includes the C16-18 fat with 30 ethylene oxide Alcohol.
12. the system as claimed in claim 1, wherein the supplement is in conjunction with carrier.
13. system as claimed in claim 12, wherein the carrier is the polymer in the group by forming as follows: poly- Alkene, phenolic resin and combinations thereof.
14. system as claimed in claim 12, wherein the carrier is the polymer in the group by forming as follows: poly- Ethylene, polypropylene and combinations thereof.
15. system as claimed in claim 12, wherein the carrier is the polymer in the group by forming as follows: poly- Styrene, polyvinyl chloride (PVC) and combinations thereof.
16. the system as claimed in claim 1, wherein the energy-storage battery component includes in the group by forming as follows Material: polyolefin, phenolic resin and combinations thereof.
17. the system as claimed in claim 1, wherein the energy-storage battery component includes in the group by forming as follows Material: polyethylene, polypropylene, polyethylene-polypropylene copolymer, polystyrene, polyvinyl chloride (PVC) and combinations thereof.
18. the system as claimed in claim 1, wherein the energy-storage battery component includes in the group by forming as follows Material: high density polyethylene (HDPE), ultra-high molecular weight polyethylene and combinations thereof.
19. the system as claimed in claim 1, wherein the supplement of the enhancing performance of the separation or synthesis passes through via choosing The technique in the lower group formed is mixed and included in together with polymer sheet forming material freely: injection molding, extrusion, burning Knot, rotational forming and blow molding.
20. the system as claimed in claim 1, wherein current turns ON suitable a period of time, wherein at described suitable one section Between be 5 hours to 1 week, wherein the electric current is suppressed before this and hereafter.
21. the system as claimed in claim 1, wherein the energy-storage battery component is different comprising naturally gathering for being obtained by rubber tree Pentadiene substance, the polyisoprene substance is in conjunction with the supplement of the synthesis of following amount: under the atmospheric pressure of 80-105kPa With 100~100 DEG C at a temperature of the energy-storage battery component comprising polyisoprene for being suitble to big fraction is placed in it is suitable Suitable a period of time and the amount by generating foam when vibration stirring are soaked in fluid, in suitable fluid, are so produced Raw foam shows the supplement of the synthesis of sufficient amount in conjunction with energy-storage battery component.
22. the system as claimed in claim 1, wherein the energy-storage battery component of selection includes selected energy-storage battery component In one or more segments, the segment be 10 millimeters or less than 100 cubic centimetres external dimensions.
23. the system as claimed in claim 1, wherein the supplement is CH3(CH2)x(OCH2CH2)y(OCH2CHCH3)zOH, It is 0 to 35 that wherein x, which is 7 to 29, y, and z is 0 to 10.
24. the system as claimed in claim 1, wherein the supplement is the rouge with eight or more and ethylene oxide Fat alcohol.
25. the system as claimed in claim 1, wherein the supplement is with eight or more and ethylene oxide and ring The fatty alcohol of Ethylene Oxide.
26. a kind of porous insulation piece, is adapted to mount between a pair of electrodes of chargeable electrochemical energy storage cell and is suitable for Separation is provided between a pair of electrodes of chargeable electrochemical energy storage cell, the porous insulation piece includes:
It is shaped to the polymer insulation piece forming material of porous insulation piece；With
The supplement of the enhancing performance of separation or synthesis, the supplement include isolated substance, the substance of synthesis or combinations thereof；
The porous insulation piece have with it includes together with formed supplement piece a certain amount of supplement, it is described with supplement The amount of piece supplement included in together be, under the atmospheric pressure of 80-105kPa and 10~100 DEG C at a temperature of will be suitable for Being partially disposed in acidic electrolyte bath of the piece for the supplement being placed in acidic electrolyte bath, soaked in acidic electrolyte bath 1-7 days with And be enough to generate the amount of foam when stirring by vibration, the foam so generated shows the supplement of sufficient amount and the piece knot of supplement It closes；And
Wherein component of the supplement in the group by forming as follows: phosphatide；Fatty alcohol alkoxy compound；Alkyl glycerol phosphorus Sour choline；With eight or more fatty alcohols；Latex obtained from rubber tree, other than polyisoprene content at Point；The alkyl amphoteric surfactant of charge is accommodated with sequence identical with phosphatide；And combinations thereof.
27. porous insulation piece as claimed in claim 26, wherein the supplement is alcohol ethoxylate.
28. porous insulation piece as claimed in claim 26, wherein the piece of the supplement is suitable for setting comprising positive electrode and negative In the acidic electrolyte bath of the electrochemical cell of electrode, to form the electrochemical cell for being combined with the processing of supplement, the place By current turns ON, the electric current is enough in response to the electric current and described the positive electrode and negative electrode of the electrochemical cell of reason Potential is provided between positive electrode and negative electrode；
Wherein, the amount with the piece supplement included in together of supplement is, when be not bound with the untreated of supplement When the performance of electrochemical cell is compared, it is sufficient to realize the electrochemical cell of the processing in the group by forming as follows extremely A kind of amount of few performance enhancement: the metal accumulation on the negative electrode for the treatment of of battery is reduced, the gas from treatment of battery escapes Reduce, the water consumption for the treatment of of battery is reduced, the potential between the positive electrode and negative electrode for the treatment of of battery increases, treatment of battery just The corrosion of electrode is reduced and the self discharge for the treatment of of battery is reduced.
29. porous insulation piece as claimed in claim 26, wherein the supplement correspond to obtained by rubber tree, in addition to Latex component outside polyisoprene content.
30. porous insulation piece as claimed in claim 26, wherein hydrophilic-lipophilic balance (HLB) (HLB) number of the supplement is big In 2.
31. porous insulation piece as claimed in claim 26, wherein the supplement also includes by the natural suitable of rubber tree acquisition Formula-polyisoprene thermo-setting elastomer.
32. porous insulation piece as claimed in claim 26, wherein the supplement includes with as the choline of head base and sweet The phosphatide of oleophosphoric acid.
33. porous insulation piece as claimed in claim 26, wherein the supplement includes with as the choline of head base and sweet Oleophosphoric acid and the phosphatide at least one saturated fatty acid and at least one unsaturated fatty acid.
34. porous insulation piece as claimed in claim 26, wherein the supplement includes with 6 to 30 ethylene oxide C8-18 fatty alcohol.
35. porous insulation piece as claimed in claim 34, wherein the supplement includes the C16- with 30 ethylene oxide 18 fatty alcohols.
36. porous insulation piece as claimed in claim 26, wherein the supplement is in conjunction with carrier.
37. porous insulation piece as claimed in claim 36, wherein the carrier includes poly- in the group by forming as follows Close object: polyolefin, phenolic resin and combinations thereof.
38. porous insulation piece as claimed in claim 36, wherein the carrier includes poly- in the group by forming as follows Close object: polyethylene, polypropylene and combinations thereof.
39. porous insulation piece as claimed in claim 36, wherein the carrier includes poly- in the group by forming as follows Close object: polystyrene, polyvinyl chloride (PVC) and combinations thereof.
40. porous insulation piece as claimed in claim 26, wherein the supplement is with eight or more and epoxy second The fatty alcohol of alkane.
41. porous insulation piece as claimed in claim 26, wherein the supplement is with eight or more and epoxy second The fatty alcohol of alkane and propylene oxide.
42. porous insulation piece as claimed in claim 26, wherein the supplement is CH3(CH2)x(OCH2CH2)y (OCH2CHCH3)zOH, it is 0 to 35 that wherein x, which is 7 to 29, y, and z is 0 to 10.
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